Soldering flux



Patented Sept. 30, 1952 UNITED STATES PATENT OFFICE 2,612,459 soi-DERTNGFLUX kHobart H.- Willard, Ann Arbor, Mich., and William; S, Gale,ySyracuse, N. Y., assigorsmto McCord Gorpoation, Detroit, Mich., acorporatin of Mairie -Nznrawiii'g Application June 2o,- 195o, SeialNo.169391 15 claims. (ci. '14s-23) This invention relates to 'sisiiieiinglfixes and for the flux' and isfevasoiated hefo'fetlie solider hasparticular reference to' nur: compositions reaches its liquidustemperaturalaving the flux,

that are especially suitable; for lsoit soldering which is generallyY arsalt or' salt nifixtiiregon the operations although the utility' of theflux commetal. When this salt or mixture' beams to melt positions is notlimited to u'se yin connection and/or decompose it reacts with theiiides or with soft soldering. other interfering lms and coatings on therha- One of the preredistes oi go'd soldering is terial to be solderedto dissolve and/or r uc the formation of a true alloyl between themetals and/ or deterge such films or coatings. Rei f being joined andthe` solder', and there; is 'some herein to the melting point orrangeerdeompoevidence that this alloyi'ng'action produces'crys- 10sition point or range of s`ol derin i'lu Vs reiers tals of aninter'metallicA compound' at the interto Vthat of substantially anhdros' face. The presence ofa oxide' coating" and other Other vehicles,such as aleo'liol; rlosinl foreign material' o nV the' surface oi the`metals to petrolatum and other materials, are ortenr be joinedseriouslyv inl'iibitsn or entirelyv prevents Although son'ie cleaningmaybe undertaken by this alloying action from taki`g"- place; It has 10the ux as applied, the real work' of removing been the practice toeriip'lyfa fluiiing agent to the oxides, films and othera coatings' fromthe remove these interfering filrn's' from the surmetal surfaces beginswhen the flux fus' face of the metals to be? joined and' the solder thiscleaning action-should@ largely A' mi)v itself. Presumably duringtriesideriiig' operaimmediately prior to the" melting i e'oldje'r. tionthe flux makes it fioss'ible for the ri'olten 30 The lowest liquidustemperature of riio'st of the solder to flow over chemically cleanedsurfaces; COmmOnly used tin-lead Soldes is above 180 however, in orderfor the solde'rt'd form analloy centigrade.- and it is thereforedesirable that the with the solder metals' it isl necessary that thenuxshould begin te melt arid/or' decompose adhesion tension betweenthemolten solder and below 180 centigrade. A f

the solid metals be greatenthan thecoliesive 25 Zinc chloride either ina Solid form Qfvih forces Within the molten' solder itself and alsoaqueous solution is in general use as' solde n g be of a higher ordervthan the adhesive'ffices ilux. It' satisfiesy several or the ne causingthe fluxv to wet the'ieteis; outlined above, but thas *the .dis/seta Theabove considerations show that" the" foldepositing iusedresidues whichrerha,in

lowing are desirable characteristics" of a ,solder- ...0. or surroundingthe joint, andth'ese" f ing flux: lsevere corrosion'unlesstheyarerein 1. The ilux shouldbe in a s'iibst'antially iluid nature of thesefused residues is such' v,

condition at temperatures'below'the'solidiistemis very difficult `orimpossible to remoyjtlfim perature of the solder and' should bein' aisubsatisfactorily, andin many` instances" Vtheir c orstantially fluidcondition throughot the" plastic 35 resi-ve action cannot be tolerated;Elunie's from range and until the molten solder' has ceasedzinc-chlorideffluxeshave a very corro ie action to flow. on jigs, xturesand other plantequi'p nt. Fur- 2. The flux should be capable of removingthermore, both theraw zinc chloride linx and oxides of metals andotherinterfering films and itsf-umes lareiparticularly dangeroilstdnr'ating coatings from the metals to be joined by'ract- 40 personnel.ling with such oxides. lrns and coatings" either A=-further objectionetothe use of zinc' chloride to dissolve, reduce or detergethesame. is thatythe vsaltdoes not use at Aa temperature 3. It should prevent the11e-oxidation of the below the melting point or the eutecticv`-' leadmetal surfaces during soldering. solder, `which is approximately' 805oemig-rade. 4f. It should be capable of'bei-ngdisplaced from 45 As mostof the commonly used tin-leadsolders the solid metal by the solderandshould vserve either are melted or their meltingrang vstarts to reducethe surface'- tension of the molten atabout .180A centigrade; it' isdesirablev tl'iatA a solder. llux whichgis to beused'efiiciently withthe yast 5. It should leave no Vresidues withinl or su-rlmajority ofthese Isoldiers should .be in' a sub'- rounding the solderedjointvvhich-w-illpromote 50 stantially lluidgconditionattemperatures-"below corrosion of the joint or surroundingv metals. 180centigrade. Since it is inthis liquid or 6. Its use should introduce:a-ffrninimum of semi-liquid condition that the luxhasheability healthhazards. to cleanthe solder-andthesurtaqes .A1-,Q b efs'oldgired,

y Fluxing agents are oftendissolvedflinwater -itshould maintain thisability untirltiiesblgr which f-unctionsmerely asf-'a cartierV orJvehicle 55- -ceasesto `flow. Ijnvorder to satisry-this" requirementsome agent is generally added to zinc chloride to form a compositionwith a lower melting point. One of the agents most commonly used forthis purpose is ammonium chloride which in itself is not a good uxingagent since it does not melt but merely sublimes.

So-called non-corrosive iluxes have been proposed to avoid some of thedisadvantages encountered in the use of a zinc chloride type iiux, andthese generally contain a salt, particularly a hydrohalogen salt, of anorganic base, and are used either by themselves or in connection With arosin type soldering flux. The fluxing action of these so-callednon-corrosive iiuxes is generally very poor in contrast to zincchloride,

and they can be shown to be corrosive under certain conditions. In manycases overheating these iiuxes causes them to sinter and they leavebehind a gummy, carbonaceous mass which is nearly impossible feres withfurther soldering to a considerable extent. The only iiux heretoforewhich could be said to be nearly non-corrosive is rosin, but rosin doesnot fulll one of the most important properties of a good iiux: namely, asolvent or slagging action metals and other coatings.

hard, lacquer-like residues left its use in many applications.

on the oxides of Additionally, the by rosin prohibit `I kIt has alsobeen heretofore proposed to use salts of hydrazine and salts ofderivatives of hydrazine as fluxes in soldering operations. The presentinvention provides improved compositions suitable for use as iiuxeswhich contain salts of hydrazine andderivatives thereof as oneingredient. The new fluxes, in comparision with those already known,possess improved properties from the standpoint of cleaning, spreading,and wetting. Additionally, they are less corrosive, and they sputterless in use. 4

We have found that these advantages can be obtained by admixing with thesalt of hydrazine or salt of a derivative thereof or a mixture of suchsalts one or more salts of hydroxylamine,

'cyclohexylamina morpholine, piperidine, ethylenediamine, ammonia, or aprimary, secondary or tertiary amine. We have also found that certaintetra-alkyl ammonium halides and lower aliphatic carboxylic acid amidescan be used to improve the properties of the salts of hydrazine or saltsof hydrazine derivatives when used as fluxes.

The following examples illustrate the preparation of variouscompositions whichV fall, within the broad scope of this invention, butare not to be considered limitative thereof.

A dry mixture composed of 40% by weight; of hydrazine monohydrochlorideand 60% by Weight of ammonium chloride was dissolved in water to form asolution containing 2% by weight of the salts. More concentrated fluxcompositions were also preparedby dissolving the dry mixture in Water toform solutions containing salt concentrations of 10% and 20% by weight.

A dry mixture composed of 95% by weight of hydrazine dihydrochloride and5% ammonium chloride was dissolved inV water to form a solutioncontaining 5% by Weight of the salts. A more concentrated ux resultedwhen the dry mixture Was dissolved in Water to form a solutioncontaining 20% by Weight of the salts.

A dry mixture composed of 98% by weight of hydrazine monohydrobromideand 2% by Weight of ammonium chloride was dissolved in water to form asolution containing 2% by weight of to remove and which intera that itshould have by weight of the salts. More concentrated fluxes 'were alsoprepared by dissolving the dry mixture in water to form solutionscontaining and 20 by Weight of the salts. These procedures were alsorepeated, but usingv dry mixtures containing 80, 60, 50, 40 and 20% byWeight of hydrazine monohydr'obromide, the remainder in each case beingammonium chloride.

A dry mixture composed of 80% by weight of hydrazine dihydrobromide and20% by weight of ammonium chloride was dissolved in water to form asolution containing 5% by weight of the salts. A flux containing ahigher concentration was also prepared containing by weight of thesalts.

A dry mixture composed of 80% by Weight of Vhydrazinebisdihydro-phosphate (HzN-NBIPOi) and by weight of ammonium chloride wasdissolved in Water to form a solution containing 10% by weight ofthesalts. A Asimilar but more concentrated ux was also preparedcontaining 20% by weight of the salts.

A dry mixture composed of 80% by weight of semicarbazide hydrochloride'and 20% by weight of ammonium chloride was dissolved in Water to form asolution containing 2% by weight of the salts. More concentrated fluxeswere also prepared by dissolving 5 Vand 10% by weight of the salts inWater. Thesey procedures were repeated using adry mixture whichcontained 40% by weight of semicarbazide hydrochloride and by weight ofammonium chloride. I

A dry mixture composed V`of by weight of semicarbazide hydrobromide and20% by Weight of ammonium chloride wasdissolved in Water to form asolution containing 2% by Weight of the salts. More concentrated uxes,were also prepared by dissolving 5 and 101% by Weight of the salts invWater. These procedures were repeated using a dry mixture whichcontained 40% vby weight of semicarbazide hydrobromide and 60% by Weightof ammonium chloride.

A dry mixture composed of 40% by weight of hydrazine monohydrochlorideand 60% by weight of ammonium` bromide was dissolved in water to form asolution 'containing 2% by weight of the salts. More concentrated uxcompositions were prepared by dissolving the dry mixture in Water toform solutions containing salt concentrations of 10% and 20% 'by weight.

A dry mixture composed of by Weight of hydrazine dihydrochloride and 5%by Weight of ammonium bromide Was dissolved in water to form a solutioncontainingl 5% by weight of the salts. A more concentrated flux resultedwhen the dry mixture was dissolved in water to form a solutioncontaining 20% by-Weight of the salts A dry mixture composed of 98% byweight of hydrazine monohydrobromide and 2% by weight of ammoniumbromide was dissolved in water to form a solution containing 2% byweight of the salts. More concentrated fluxes' were prepared bydissolving thev dry mixture 'in water to form solutions containing 10%and 20% by weight of the salts. These procedures were also repeated, butusing dry mixtures containing 80, 60, l50, 40 and 20% byl Weight ofhydrazine monohydrobromide, the remainder in each'ca-se being ammoniumbromide.

A dry mixture composed of 40% by Weight of hydrazine monohydrochloride,30% by weight of ammonium chloride and 30% by Weight of ammonium bromidewasdissolved in water to form Weight of hydrazine,

2.5 %fby weight esitare ai solution containing' 2 %^"by."weight' or vthesalts. Additional` fluxes werealso `prepared containing loand 20%. byweight ofthe dry mixture. l

lA dry mixture was prepared containing 80 by monohydro'chloride and 20%by 'weight of monoethylamine hydrochloride. Portions ofthis mixturewereldissolved'in'water to form 5, and 20% byw'eight'isolutions, andthese procedures were 'also' repeatedw using a`r drymixture. containing50 %'by weight of hydrazine monohydrochloride and 50%bywei'ght'ofm'onoethylamine 'hydrochloride'.

A' dry 'mixture'wa's prepared'containing 80% yby f weight' of vhydrazinemonoiiydrobromide' and20 byfweight Aoi'vj 'mono-ethylamine'hydrochloride.

Portions of this" mixture were dissolved in water to form 5;li0fa.nd'200/ 'byweightsoiutions and these procedures were "also"repeated* using7 a' dry mixture containing 50% 'byweighify of hydrazinemonohydrobrornide and 50 %"by'-weight 'of mono-f ethylaminehydrochloride. i

Al dry mixturewas prepared containing 80% by weight ofhydrazine-monohydrobromide'fand 20% by weight ofdiethylaminehydrochloride: Portionsof this mixture were'dissolved inwater'to form 5,' lo and 20% byl weight solutions', andthese procedures*werev f also repeatedy using' a` dry mixture containing-'501% by Weightof' hydraz'ine monohydrobromide and-50%`1 b y weight of diethylaminehydrochloride.

A-dr'y mixture -wasprepare'dcontaining 80 by weight ofhydrazinemonohydrobromide and by r weight 'oi i triethylamine'hydrochloride.' Portions 'oii this mixtureiiwere dissolved'lin water. toform 5, 10 and' 20%` by weight' solutions, andl these procedures werealsorepeatedusing a dry mlxture'containing 50% by weight-.ofhydrazinemonohydrobromide and 50% by'weight oftriethylamine hydrochloride.

A dry mixture was prepared containing. by

10% by Weight solution.

Weightohydrazine monohy'dr'obromide and 20% by weight ofethyienediaminel hydrochloride. This` mixture was dissolvedV inWater-toA form a 10%* by weight solution'.-y v

Ar dry Ymixti'irje was prepared ycomposed of i80byfwei'ght'foifhydrazine dihydrochiori'de and 201% by weight of"morpholin'e' hydrochloride. rlhis mixture was I weight solution.

20%y by'- vveight 'of' Weight of hydrazine monohydrobromide,l 25% by vweight of hydrazine monohydrochloride, and 50% byu/eight ofammoniurnchloride.v Portions of this dry mxturevwere dissolvedinwaterto formlOand 20% by. weightsolutions.

A dry mixturel Wasprepared containing., 25% by Weight ofsemicarbazide.'hydrobromide, .25%

-by Weight of lhydrazine monohyd'rochloride, and

50% by weightoiamrnonium chloride. Portions of 'this dry mixture were"dissolved inl Water to form 10 and-20%by weight solutions.

A dry mixture, waspreparedcomposed of 95 byvveight of hydrazinedihydrob'romide,-2l5'% by weight ofhydrazine rnonohydrobromidefI and ofammonium bromide. Portions' of thisdry mixturewwere dissolved in. Waterto form 2; 10` and 20% by, Weight solutions... procedures were alsorepeatednsing a-dry vmixture composed of 20% by Weight oi hydrazinedihydrobromide, 60% byweight ofhydrazine monohydrobromide, and. 20 r byweight -o ammonium bromide. A dry' mixture was preparedcomposed of 45%of hydrazine monohydrobromid'e, zine'dihydrobromide, 5% of ammoniumbromide, and of ammonium chloride byiweight. Portions of this drymixture were dissolved in `Water toform 10 and 20 %"by weightfsolutions.

A dry mixture Wasprepared containing '15%' by lweight of*Ll-dimethylhydrazine hydrochloride and 25% by'weightof ammoniumchloride. This dry mixture was 'dissolvedin Water to form a 20 l byweight solution.

. formula. RiRaN-NRsRi are A dry-mixture'. was preparedcontaining 70%'by 'WeightV of methylhydrazine hydrochloride and whereinT R1 is analkyl,

used, there can be mixture was dissolved' in'Waterto-forni' a 10% by'kWeight solution.A

A dry mixture Waspreparedoompose'd'of' 80% by weight of hydrazinemonohydro'ohloride and v tetramethyl ammonium chloride.l This mixturewas dissolvedfinfwater to form af10% by' Weightsolution.V

A dry mixturev was .preparedzcomposed of.50% by' Weight! of hydrazineniohohydrobromider and 50% by Weight of'hydroxylamine hydrochloride.

'This `mixture was dissolved` in Water to form a 10%'bylweight'solution.

' Various *modications' can be made' in the teachings of the specificexamples 'to providey other compositions `vvhi'ch ialllSW-thin theIbroad scope of the present invention'. Thus; in place of the particularsalts of'hydrazineused'there can' be substituted one" or morecorresponding fs'alts of'organic derivatives ofhydra'zine, 'whichderivatives 'fall Within the' general lfo'rinula aralkyl' or arylhydro'- carbon radical and R2, R3 andRi are hydrogen atoms oralkyl,`aralkyl or aryl' vhydrocarbon radicals. Amongy thehydrocarbonsubstituents which can suitably be present inthe compoundofthe the methyl, ethyl, normal propyl, isopropyl, normal butyl',isobutyl, secondary butyl, benzyl, phenylethyl, phenyl,orthotolyL'metatolyl, oals. Thus, in place of the particular hydrazinesalts used according' to theY specific examples there can be substitutedthe corresponding salts of symmetrical dimethyl hydrazine, unsymmetricaldimethyl hydrazine, trimethyl hydrazine,

Also, in place of the particular 'hydr'azine salts substituted one or'morel other saltsllthereof, such as hydrazine.'dihydrofluoride,`hydrazine 'dihydroiodida trihydrazine dihydroiod ide,` hydrazinephosphate (NHr-NHrfHdPO-i), hydrazine hypophosphate (NH-NHzfHiPzOQg'hydrazine for-mate NH2-NHi-2Hcoon), hydrazine acetate(NHz--NHz-'2CI-I3`COOH) hydrazine oxalate (NHz-NHzHsC'zOO andhydrazineparatolyl andthe xylyl radil of semicarbazide disclosed general, thecompositions by weight of the salt or salts 7 l Further, in addition to`the particular-salts amples there can be substituted othersem-icarbazide salts,.such as semicarbazide hydroiiuoride andsemicarbazidephosphate l j (NI-IzNI-ICO'NI-Ia-HSPOD n' Y In addition, inplace of the Yammonium and amine salts disclosed lin the-examples,therevcan be used the corresponding salts of one or more other amines,such as cyclohexylamine, `piperidine and other amines falling Within thescope of the formula RsRsRiN wherein R is an alkyl, aralkyl or arylhydrocarbon radical and wherein Re and Rv are a hydrogen atom or analkyl, aralkyl or aryl hydrocarbon radical. Thus, among the suitablesubstituents which can be included in the compound of the formula RReRvNare the methyl, ethyl, normal propyl, isopropyl,

normal butyl, isobutyl, benzyl, phenylethyl, phenyl, orthotolyl,metatolyl, paratolyl and the xylyl radicals. y i

Alcr example, among the suitable amines which can be used in the form oftheir salts are methylamine, dimethylamine, trimethylaminemethylethylamine, triethylamine, monoisopropylamine, diisopropylamine,-benzylamine, .aniline, orthotoluidine, metatoluidine, the Xylidines,methyl phenylamine, dimethyl phenylamine, etc.-

Further, in place of the tetramethyl ammonium chloride used there canvbe substituted one `or more other tetra-alkyl ammonium halides whereineach alkyl radical contains from one to two carbon atoms, for example,tetraethyl ammonium bromide. The use of other ammonium salts is alsoincluded within the scope of `this invention,l for monium formataandammonium phosphate, as is the use of aliphaticcarboxylio' acid amidescontaining from one "toiour carbon atoms, for

example, `formamidejand propionamide.

in the yspeciiicpex- Y example, ammonium carbonate, am-

' present invention.

As the speci-fic illustrations above teach,V it is y convenient todissolve vthe anhydrous 'uxes of our invention in a suitable solvent in.which `the iiuX as solute constitutes 0.5% to 20% by Vweight of thetotal resulting solution. However,the only upper limit of thisconcentration is the solubility of the anhydrous material in thesolvent. In some applications'it is `desirable `for a soldering iiux tobe supplied in a` paste form, and thisy is usually' accomplished byintimately mixing the fluxing agent in a plastier, such as petroleumjelly, rosin, and various other compounds. It is possible to makeadditions of the fiuxesv of our invention to such compositions, andsuitable percentages are those within the range from 0.5%

to 10% of Vthe total composition |by weight.

As an xplanation of the Wide variances in the percentages listed in theexamples, it is rnecessary to consider the particular metals .heiligsoldered, their surface condition, and the function that 'the joint ynature of certain soldering operations and joints to be soldered is suchthat fluxes withvslightly different melting and/or decompositionV`characteristics are essential to eiiicientsoldering'. "In

of the present inven- 20 to about 98% of hydrazine or hydrazinederivatives, based upon the Weight of such salt or salts and theammonium salt, the

tion will contain from about :amine salt-thetetra-alkyl ammoniumhalideand aliphaticcarboxylic acid amide. Although the flux compositionsembodying our invention are suitable for use in soldering most willperform in service. The

Y Soldering Flux.

' in the range from weight of said two components.

ofthe commonly used'metals, such as copper, brass,l bronze,aluminum,'zinc,"tin or galvanized surfaces, and iron'y and steel andtheir alloys, it

has been found'that by taking into consideration the propertiesvandco'ndition of the metals to be soldered,vmore effective vresultsmaybe obtained withcertain of the'iiuxfconpo'sitions herein disclosedthan 'with` others. 1

The composition of the present invention, when :employed as'aiiuxjinsoftsoldering, is used in rated into flux compositions, and, if desired,such agents can also be incorporated in the ux of the Theluse of one ormore salts of ammonia or of an amine or .the tetra-alkyl ammonium halideor the lower yaliphatic carboxylic acid amide resultsk in a decrease inthe ratev at whichgas is evolved from the mixture with respect toincrease in temperature.. Since the evolution of gasffrom the mixtureisa manifestation of decomposition,

it is possible to increase the temperature atwhich final decompositionwill takefplace. As ,a result oi' increasing the range .of4 temperatureover which the flux composition is active, it is possible to increasethe area over whichithe molten solder-will spread, therebyobtainingimproved soldering.

' This application isa continuation in part of our prior vcopending.application, Serial No. 113,672, filed September v1, '1949, nowabandoned, .for

We claim:

1. A compositionof matter vsuitable for use as a solderingf'flu'xcomprisingfessentially, as a first componentfatleastonesalt of acompound of the class consisting; of se'micarbazide and RlRzN- NRsR4 inwhich R1, 'RaRe and R4 are/,substituents vselected from'the groupconsisting of the hydrogen atom and alkyl, aralkyland aryl hydrocarbonradicals and; asa second component, at least one compound'selectedffrornthe group consisting of'k mg o f the hydrogen atoin'and alkyl,aralkyland aryl hydrocarbon radicals, and RaRQRmRnNX in which RB, Rg,amend R11 aresubstituents selected from the group consisting of themethyl Vand ethyl radicals and in which Xis a halogen atom, the weightof said'second component being with- 2. A composition as in claim 1 inwhich'said rst component is at least one saltr ofhydrazine. 3.` Acomposition as in claim 1 in which said second component is ,atV leastone salt of ammonia.

4. A composition as in claim 1in which said -rst component isv atleastone salt of hydrazine and inrwhich said secondcomponent is at leastone salt of ammonia.

5. .A composition as nl daim 1 in which saidl :,nrst vcornponents amixture of 'hydrazine monohe'work has beencooled,

{%,} based upon the hydrqbrornide and hydrazine dihydrobromide and inwhich said second component is ammonium bromide.

'1. A composition as in claim 1 in which said first component is amixture of hydrazine monohydrobrqmide and hydrazine dihydrobromide andin which said second component is a. mixture of ammonium chloride andammonium bromide.

8. A composition as in claim 1 in which said first component ishydrazine monohydrobromide and in which said second component isammonium bromide.

9. A composition as in claim 1 in which said first component ishydrazine monohydrobromide and in which said second component isammonium chloride.

10. A composition as in claim 1 in which said first component ishydrazine monohydrobromide and in which said second component isamixture of ammonium chloride and ammonium bromide.

11. In soft soldering, the step of applying to the metals to be joinedthe composition defined by claim 1.

12. In soft soldering, the step of applying to the metals to be joinedvthe composition defined by claim 2.

13. In soft soldering, the step of applying to the metals to be joinedclaim 3.

the composition defined by 10 14. In soft soldering, the step metals tobe joined the composition claim 4.

15. In soft soldering, the step of applying to the metals to be joinedthe composition defined by claim 5.

of applying to the dened by HOBART H. WILLARD. WILLIAM S. GALE.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,882,734 Barber Oct. 18, 19322,089,095 Magill Aug. 3, 1937 '2,155,307 Hagemann Apr. 18, 1939 FOREIGNPATENTS Number Country Date 677,994 Germany July 6, 1939 '751'370 FranceJune 19, 1933 OTHER REFERENCES Mellor, Comprehensive Treatise onInorganic and Theoretical Chemistry, vol. VIII, page 328, published1928, by Longmans, Green and Co., New York,

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